Coagulation Kinetics of Humic Aggregates in Mono- and Di

Article
pubs.acs.org/est
Coagulation Kinetics of Humic Aggregates in Mono- and Di-Valent
Electrolyte Solutions
Long-Fei Wang,† Ling-Ling Wang,† Xiao-Dong Ye,‡,* Wen-Wei Li,† Xue-Mei Ren,§ Guo-Ping Sheng,†
Han-Qing Yu,†,* and Xiang-Ke Wang§
†
Department of Chemistry, ‡Department of Chemical Physics, University of Science & Technology of China
Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, 230026, China
§
S Supporting Information
*
ABSTRACT: Coagulation behaviors of humic acids (HAs) aggregates in
electrolyte solutions at different pHs, valences and concentrations of electrolyte
cations were investigated using dynamic light scattering technique in
combination of other analytical tools. For monovalent electrolyte sodium
chloride (NaCl) solution, at its low concentrations the average hydrodynamic
radius (<Rh>) of aggregates kept nearly constant. However, at high NaCl
concentrations, <Rh> could be scaled to the time t as <Rh> ∝ ta, suggesting a
diffusion-limited colloid aggregation (DLCA). The coagulation value of NaCl in
a buffer at pH 7.1 was calculated to be in a range of 61.3−84.4 mM. Divalent
cation Mg2+ was far more effective in enhancing the HA coagulation, as
evidenced by a lower coagulation value (between 1.0 and 1.7 mM) and a more
rapid coagulation rate. Such an enhancement could be explained by the
combined effects of electrostatic repulsion, complexation and bridging. The
highest coagulation rate (d<Rh>/dt) and coagulation value at different pHs followed the order of: acidic > neutral > alkaline, and
alkaline > neutral > acidic, respectively. Such a difference was associated with the extent of hydrogen bond and electrostatic
repulsion at different protonation/deprotonation states of carboxyl and phenolic −OH groups. Transmission electron
microscopic imaging reveals that HA was predominantly globular aggregates with a rough periphery at pH 5.26, and was changed
to smooth spherical particles at pH 10.00. These results are useful for better understanding the coagulation behaviors of HAs in
both natural and engineered aqueous systems.
■
spectroscopy,3,8,9 capillary zone electrophoresis,10 nuclear
magnetic resonance,11 surface tension measurements,12,13 and
dynamic light scattering (DLS).14−16 For example, the
fluorescence correlation spectroscopy revealed that the
disaggregation rate of HA particles was strongly dependent
on pH.3 Among these techniques, DLS offers a powerful tool to
determine the size distribution of nanoparticles in suspension
and polymers in solution and has been used to explore the size,
fractal characteristics, and coagulation kinetics of HAs.14−17
The physicochemical properties of HAs, such as their
inherent biopolymer chain structure and colloidal characteristics, are related highly to the solution chemistry, for example,
electrolyte and pH. The ionized and un-ionized states of
functional groups including carboxyl and phenolic −OH, which
vary considerably with pH change, significantly influence metal
complexation, surface charge, and supramolecular structure.4,18−20 For example, formation of negative charges due to
ionization of carboxyl groups is responsible for the mutual
repulsion and expansion of coil.18 It is found that electrostatic
INTRODUCTION
Humic substances (HS) are formed from biochemical weathering of plants and animal remains and are widely present in
nature.1,2 As a principal component of HS, humic acid (HA)
has many unique properties, for example, insoluble at pH < 2,
but soluble at higher pHs, and has been implicated in both
engineered and natural processes. One promising application
direction is for environmental pollutant removal and a
profound impact of HA on the transport, sequestration, and
mitigation of environmental contaminants has been well
recognized.2−4 Especially, HAs tend to coagulate, and the
aggregated HA molecules are found to trap a considerable
amount of contaminants and thus weaken the degradation and
neutralization of contaminants.4 In addition, the colloidal
aggregates of HA confer excess potential binding sites for many
materials, for example, metals, clay particles, and pesticides.4
Apparently, the coagulation of HAs remarkably influences their
interactions with contaminants in aqueous/soil systems and is
of great significance for environmental remediation. Thus, an
exploration into the coagulation mechanisms of HA has
attracted intensive interests worldwide.
The aggregation/coagulation of HAs has been studied with
several techniques, for example, fluorescence spectroscopy,5
atomic force microscopy,6 turbidity,7 fluorescence correlation
© 2013 American Chemical Society
Received:
Revised:
Accepted:
Published:
5042
December 20, 2012
April 8, 2013
April 17, 2013
April 17, 2013
dx.doi.org/10.1021/es304993j | Environ. Sci. Technol. 2013, 47, 5042−5049
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major element compositions and the high-resolution scan (70.0
eV pass energy) for component speciation.
FTIR measurements were carried out with VERTEX 70
FTIR (Bruker Co., Germany). For each sample, approximately
5 mg of HA was dissolved in Millipore water. The solution pH
values were adjusted to 1.70, 5.25, and 10.04 with 0.2 M HCl
and NaOH solutions, respectively. Lastly, the samples were
mixed with KBr powder for FTIR analysis after lyophilization.
Acid−base titration was carried out using an automated
titrator (DL50 Mettler-Toledo Inc., Switzerland) at 25 °C. HA
at a concentration of 1250 mg L−1 was dissolved in Millipore
water. Before titration, a given amount of 0.1 M HCl was added
to lower the pH to below 3.0. The solution was initially stirred
for 20 min and then titrated with 0.09 M NaOH solution under
N2 atmosphere programmed in incremental monotonic mode
with a dosing unit of 8 μL. The titration data acquired were
analyzed with the PROTOFIT 2.1 software by using the
Donnan Shell Model.29 The titration results were also
compared with the NICA (nonideal competitive adsorption)
−Donnan simulations of reported HAs detailed in Supporting
Information (SI).
DLS and Electrophoretic Mobility. DLS measurements
were conducted using an ALV/DLS/SLS-5022F spectrometer
equipped with a multi-τ digital time correlator (ALV5000), and
a cylindrical 22 mW UNIPHASE He−Ne laser (λ0 = 632.8 nm)
as the light source at 25 °C. The glass vials (27150-U, Supelco
Co., Bellfonte, PA) used were cleaned in piranha solution (1:3
vol/vol of 30% hydrogen peroxide and concentrated sulfuric
acid) and then thoroughly leached with distilled acetone. For
each sample, 2 mL of HA solution at a concentration of 100 mg
L−1 in designed buffers was filtered into one dust-free vial with
a 0.45 μm hydrophilic PTFE (Millipore Millex-LCR) and left
overnight. A certain amount of electrolyte solution with diverse
concentrations was filtered into the HA solution. The vial was
placed in a sample holder without further stirring and the
scattered light intensity was adjusted before each measurement.
The weights before and after the dose of electrolyte solution
were recorded so that the exact electrolyte concentration in
each vial could be calculated.
The scattering angle was set at 90° and duration of a single
measurement was 30 s. In DLS, the Laplace inversion of a
measured intensity−intensity time correlation function
G(2)(t,q) in the self-beating mode can result in a line-width
distribution G(Γ) by CONTIN method. For a pure diffusive
relaxation, Γ is related to the translational diffusion coefficient
D by Γ/q2 = D at q → 0 and C → 0. In this study, no
extrapolation of q → 0 and C → 0 was done and an apparent
hydrodynamic radius Rh = kBT/(6πηD) was determined, with
kB, T, and η being the Boltzmann constant, absolute
temperature, and solvent viscosity, respectively.30 As the
scattered light intensity should be adjusted before each
experiment, the time between the injection of electrolyte
solution and first measured value was controlled close to 120 s.
The coagulation kinetics was examined without stirring. In
addition, the measured correlation functions were also analyzed
by the cumulant method, and the two methods showed similar
results. The polydispersity indexes (PDI) derived from the
cumulant analysis were less than 0.3, indicating the results were
fairly reliable.31
The electrophoretic mobility of each sample was recorded
using a Nanosizer ZS instrument (Malvern Instruments Co.,
UK) equipped with backscattering detection at 173° and 25 °C.
HA was dissolved in pH 7.1 Tris-HCl buffer to reach a final
interactions play a predominant role in the colloidal stabilities
of HA and that its aggregation is governed mainly by the
screened electric field developed from the dissociation of acidic
groups bound to the cross-linked polymeric network of HA
molecules.21 Theoretical explanations for the sensitivity of
colloidal stability as a function of pH and electrolyte have also
been provided.22 Na+ and Mg2+ are among the most abundant
cation ions in natural waters23 and HA can cause severe
membrane fouling problems in engineered filtration processes.24,25 An investigation into the coagulation of HA in
electrolyte solutions might aid a better understanding of the
membrane fouling caused by HA in seawaters as well as in
freshwaters, especially in the case of eutrophication.24−26 The
condensed HS at acidic-pH landfill leachates and mining
effluents may significantly affect a wide range of geochemical
processes, such as humic−metal complexation and pollutant
detoxification.27
However, so far most studies concerning HA aggregation/
coagulation were conducted under equilibrium or near
equilibrium conditions.3,5−8,10−13 The HA coagulation kinetics
and the effects of cation valence and solution pH on HA
coagulation behaviors (e.g., coagulation kinetics, rate of early
stage, and final aggregate size) have not been thoroughly
understood yet.
In this work, DLS analysis was performed to explore the
coagulation behaviors of HA in monovalent and divalent
electrolyte solutions. The chemical elements, functional groups,
structure information were comprehensively identified using
combined techniques, including Fourier transform infrared
(FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS)
and acid−base titration. Typical monovalent (NaCl) and
divalent (MgCl 2 ) electrolytes were applied to induce
coagulation of HA in buffers at different pHs. The coagulation
kinetics in the presence of NaCl at pH 7.1 was fitted with
typical diffusion-limited colloid aggregation (DLCA) model.
The coagulation behavior of HAs governed by solution
chemistry was examined in terms of their colloidal properties,
and was elucidated from a physical chemistry point of view. In
addition, transmission electron microscope (TEM) was used to
image the morphology of HA colloids.
■
MATERIALS AND METHODS
HA and Solutions. AR-grade electrolytes (NaOH, HCl,
NaCl, and MgCl2) at various concentrations were prepared and
filtered with 0.22 μm filter prior to use. Buffers used in this
study were prepared with Millipore water according to Rex et
al.: glycine-HCl for pH 3.6, Tris-HCl for pH 7.1, and glycineNaOH for pH 10.0.28
Commercial HAs purchased from North China Chemical
Reagent Co., China, were purified1 prior to use as a model to
study the coagulation behaviors of natural organic materials. 10
g of HA was dissolved in 1 L of 0.1 M NaOH and then filtered.
The solution was acidified to pH 1.0 using concentrated HCl
solution and filtered. The precipitates were washed with 0.1 M
HCl for three times and lyophilized. Such purified HAs were
dissolved in buffers to reach a final concentration of 100 mg L−1
and left for 12 h to reach complete dissociation.
XPS, FTIR, Acid−Base Titration. XPS (ESCALABMKII,
VG Co., UK) was used to examine the elemental compositions
and functional groups. Survey and high-resolution scans were
collected using pass energies of 20.0 and 70.0 eV, in which the
broad survey scan (20.0 eV pass energy) was conducted for
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concentration of 200 mg L−1. HA solution and NaCl solution at
different concentrations were mixed at equal volume and
measured. Each sample was measured at least 6 times and data
were presented as mean ± standard deviation.32,33
Coagulation Kinetics Analysis. According to the classical
DLVO theory, the energy of interaction between two
approaching particles plays a key role in coagulation.34 Two
regimes of irreversible colloid aggregation, that is, reactionlimited colloid aggregation (RLCA) and diffusion limited
colloid aggregation (DLCA), have been identified. DLCA
occurs when there is negligible repulsive force (e.g., in solutions
at a high electrolyte concentration) and the aggregation rate is
limited solely by the time taken for clusters to encounter each
other by diffusion.34,35 On the other hand, RLCA occurs when
there is a substantial but not insurmountable repulsive force
between particles.35,36
The coagulation process can be reasonably described by a
power-law equation as a function of time, that is, R ∝ ta in
DLCA regime, and an exponential equation in RLCA
regime.35−37 The reverse of the exponent is defined as the
mass fractal dimension (df = 1/a), which can be used to
describe the scaling behavior of highly disordered structure of
colloidal aggregates.36,38 The df reflects the actual space
occupied by the system and characterizes the degree of
“openness” of the fractal structure.39 Any object in a real
physical process must have a mass fractal dimension 1 ≤ df ≤ 3.
A lower df means that the penetration of particles into a fractal
cluster is more efficient. The typical mass fractal dimension is df
≈ 1.8 for DLCA, and df ≈ 2.1 for RLCA, indicating a more
compact structure in RLCA.35,39
TEM Observation. To prepare TEM images, the HA
powders were dissolved in Millipore water to a concentration of
100 mg L−1. Then, the pH values were adjusted to 5.26, 7.00,
and 10.00 with dilute HCl and NaOH solutions, respectively.
Several drops of each sample were added onto copper grids. To
ensure the HA colloids to keep their original morphology to the
largest extent, copper grids were instantly frozen in liquid
nitrogen, followed by lyophilization.
the NICA-Donnan simulation results of the reported HA (SI
Figure S3).
HA Coagulation in NaCl Solution. Figure 1 illustrates the
<Rh> changes of HA aggregates as a function of time and NaCl
Figure 1. Coagulation profiles of HA aggregates as a function of time
over a range of NaCl concentration from 38.6 mM to 380.5 mM at pH
7.1.
concentration. At a low concentration of NaCl (0−61.3 mM),
<Rh> remained about 50 nm, indicating the stability of HA
colloids. The z-mean of the square of the radius of gyration
(Rg) of HA molecules is reported to be 4−10 nm,19 much
smaller than the size of the stable HA colloids (52 nm) in this
study. In a similar work, Pinheiro et al. reported initial
aggregate sizes for peat HS in a range of 30−185 nm.14 Thus,
HA colloids can be regarded as an entity of small aggregates
here. When the NaCl concentration was further increased from
84.8 to 380.5 mM, the stability of colloids was destroyed.
Ultimately, coagulation occurred as indicated by the rise of
<Rh>.43 The characteristic aggregate sizes in each profile were
applied to fit with typical power-law function of the DLCA
regime to obtain the most optimum coagulation kinetics. The
fitting details are given in Table 1. The initial <Rh> was fixed as
the average value of 52 nm in the presence of 61.3 mM NaCl.
■
RESULTS
Physicochemical Properties of HA. The XPS results
show that the elemental composition of C, O, N, and S were
69.80%, 24.99%, 4.88%, and 0.33%, respectively. The detailed
XPS analysis results are provided in SI Figure S1 and Table S1.
The FTIR spectra of HAs show typical functional groups in SI
Figure S2 and the assignments given to the various bands are
tabulated in SI Table S2. By comparison, one significant
difference between the spectra was the loss of the −COOH
band at 1720 cm−1 in alkaline solution as a result of
deprotonation of −COOH.1,40 Peak intensity in a range of
1280−1200 cm−1 reflected the extent of H-bonds,40 whereas
the reduction of intensity at pH 10.04 corresponded to the
deprotonation of H-bonds.
In HS-related studies, the concentrations of main functional
groups, that is, carboxyl and phenolic −OH, have been
measured and reported.41,42 From the titration data, the
Donnan shell model with two discrete sites was applied to
simulate our results.29 The pK values of carboxylic and phenolic
−OH groups were estimated to be 5.08 and 7.96. The site
densities were calculated to be 3090 and 1050 mmol kg−1dw for
the carboxylic and phenolic −OH groups, respectively (SI
Table S3). The titration data were generally in agreement with
Table 1. Coagulation Kinetics for HA in Tris-HCl Buffer
(pH 7.1)
parameters
NaCl
(mM)
94.4
119.0
178.7
380.5
optimum
kinetics (R0 =
52 nm)
R = b·ta + R0
a
b
df (fractal
dimension)
adjusted
R2
0.50
0.44
0.46
0.45
18.0
33.1
32.4
31.9
2.00
2.27
2.17
2.22
0.957
0.914
0.940
0.942
regime
DLCA
To test the variations of <Rh> in coagulation, the timedependent hydrodynamic radius distributions f(Rh) were
calculated by CONTIN algorithm. The results are shown in
Figure 2, taking the 119 mM NaCl profile as an example. The
shift of the peak indicates the growth of HA colloid size in
coagulation.44 It is worth noting that a broader distribution
means a larger difference in <Rh>.30 The width of the
distribution function increases as a function of time, which is
consistent with the observation in Figure 1, in which HA
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Figure 2. Time-dependent hydrodynamic radius distributions f(Rh) for
HAs in 119 mM NaCl solution at pH 7.1.
aggregates were found to exhibit more randomly fluctuating
<Rh> at later stages. At the final coagulation stage, also called
quasi-steady state, aggregates continued to grow at a slower rate
than the early linear growth stage. This coagulation progress
was likely governed by larger aggregate-aggregate interactions
and collisions, resulting in a much wider distribution of <Rh>.44
Coagulation value is defined as the minimum concentration
of the electrolyte required to cause coagulation of colloids.34
Figure 1 shows that the coagulation value was in a range of
61.3−84.8 mM. HA coagulation in acidic and alkaline buffers
(pH 3.6 and 10.0) induced by NaCl was investigated (Figure 3
and SI Figure S4). At pH 3.6, HA quickly coagulated at a rather
low NaCl concentration. In alkaline solution, more electrolytes
were needed to induce the coagulation, confirmed by the
highest coagulation value (116.0−127.6 mM). Considering the
background ionic strength of buffer solutions, the coagulation
values of the three solutions were in the order of: alkaline >
neutral > acidic. For each pH, a typical coagulation profile was
selected to represent the early coagulation rate of HA (Table
2). The typical coagulation rate at pH 3.6 was almost an order
of magnitude higher than that at pH 10.0 even at a much lower
electrolyte concentration (22.4 mM compared to 127.6 mM).
In a similar work to evaluate the influence of pH on HA
diffusion coefficient,14 Pinheiro et al. found that at pH < 2.5,
coagulation occurred quickly, leading to the precipitation of
HA. A noticeable decrease in size was observed after pH was
increased from 4.0 to 6.0.14 A significant variance was also
observed for the final maximum aggregate <Rh>, which
decreased from 1452 nm at pH 3.6 to 528 nm at pH 10.0
(Table 2).
HA Coagulation in MgCl2 Solution. To evaluate the
effect of cation valence on the coagulation behaviors, HA
coagulation in MgCl2 solutions with a concentration from 0.2
to 2.0 mM was evaluated. Tris buffer, which shows negligible
metal binding effect at 20 °C, was selected as the solvent.45
Figure 4 shows that at a concentration lower than 1 mM, the
<Rh> remained almost constant, while a rapid rise of <Rh> was
observed when the MgCl2 concentration exceeded 1.7 mM.
Compared with Figure 1, a much lower concentration of Mg2+
than Na+ could induce a drastic HA coagulation. From the
Schulze-Hardy rule, the theoretical coagulation value is
determined by the valency of the ions, which are oppositely
Figure 3. Coagulation profiles of HA aggregates as a function of time
over a range of (A) NaCl concentration from 116.0 mM to 453.3 mM
at pH 10.0; and (B) NaCl concentration from 1.1 mM to 47.3 mM at
pH 3.6.
charged to the colloidal particles.34 (proportional to z−6 for
particles, where z is the valence of cation)
M +: M2 + = 16 :
⎛ 1 ⎞6
⎜ ⎟
⎝2⎠
(1)
The coagulation value of NaCl in the same buffer was in a
range of 61.3−84.4 mM. In contrast, the coagulation value of
MgCl2 was calculated to be within 0.96 and 1.33 mM, which is
in the range of the experimental data. The final maximum
aggregate <Rh> was 1583 ± 131 nm in the presence of 2 mM
MgCl2. The dose of 2 mM Mg2+ caused an intense fluctuating
radius in the final coagulation process (Figure 4), which is
similar to the later coagulation stages shown in Figure 2.
Electrophoretic Mobilities of HA. Figure 5 presents the
electrophoretic mobilities of HA in pH 7.1 Tris-HCl buffer over
a range of NaCl and MgCl2 concentrations. All the samples
were negatively charged. As the NaCl concentration was
increased from 5 to 100 mM, the electrophoretic mobility
tended to be less negative as a result of charge screening effect.
This phenomenon has been commonly observed for other
colloidal aggregates.32,33 Figure 5 also shows that, compared to
monovalent Na+, Mg2+ was much more effective in reducing the
electrophoretic mobility of the HA aggregates.
TEM Observations. TEM imaging illustrates that HAs were
colloidal-sized macromolecules with variable structures at
different pHs. Their macromolecules were predominantly
globular aggregates with ring-like structure of rough periphery
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Table 2. Typical Coagulation Rates and the Final Maximum Aggregate <Rh>
final maximum aggregate <Rh>
typical coagulation rates (data from 120 to 820 s)
pH
3.6
7.1
10.0
7.1
(d<Rh>/dt)
(nm/s)
<Rh> at 120 s
(nm)
adjusted
R2
corresponding conc.
(mM)
1.34 ± 0.05
0.90 ± 0.06
0.15 ± 0.01
120
171
113
0.979
0.938
0.982
22.4
119.0
127.6
average of last ten <Rh>
(nm)
corresponding conc.
(mM)
±
±
±
±
22.4
178.7
337.2
2.0
1452
1283
528
1583
88
60
24
131
electrolyte
NaCl
MgCl2
Figure 4. Coagulation profiles of HA aggregates as a function of time
over a range of MgCl2 concentration from 0.2 mM to 2 mM at pH 7.1.
Figure 6. TEM images of HA at pH: (A) 5.26; (B) 7.00; and (C)
10.00 after instant freezing in liquid nitrogen, followed by
lyophilization.
Figure 5. Electrophoretic mobilities of HA solution as a function of
electrolyte concentration in pH 7.1 Tris-HCl buffer. Each data point
represents the mean electrophoretic mobility. Error bars represent
standard deviations.
understanding the transport and fate of pollutants.1,2,4
However, the coagulation kinetics of HA and the influences
of solution chemistry have not been thoroughly understood.
For both natural and engineered aquatic systems, common
discrepancy in electrolyte might result in different solution
chemistry. Thus, typical monovalent and divalent electrolytes,
that is, NaCl and MgCl2, were selected to study their impacts
on the HA coagulation.
HAs are a basically heterogeneous mixture of polyelectrolytic
organic molecules and exhibit a continuous distribution of
molecular and structural properties. Since they show polydispersity and mass fractal features in solution, the
interpretation of DLS data might be complicated.7,17 However,
polydispersity is found to have no significant effect on the
aggregation of colloids and calculated Df.47,48 Power-law
at pH 5.26 (Figure 6A), similar to the HS morphology
observed at pH 3.0 ± 1.0.46 As pH was increased to 7.00, the
periphery became less rough and more globule-like. The HA
macromolecules changed to smooth spherical particles with a
radius of approximately 50 nm (Figure 6C) at pH 10.00. This is
consistent with the average hydrodynamic radius (52 ± 2 nm)
determined by DLS.
■
DISCUSSION
HA Coagulation Mechanisms in Electrolyte Solutions.
The coagulation of colloidal HA is of great importance in
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gressively more important at a low pH.53 The dissociation
degree of functional groups of biopolymer chains depends
largely on the solution pH.54,55 The colloidal stabilities would
be significantly different at different pHs as the electrostatic
field is developed from proton dissociation of acidic groups.21
At pH 3.6, strong intermolecular hydrogen bonds hold HA
molecules together. The presence of protonated −COOH is
confirmed by the FTIR analysis (SI Figure S2). Thus, a rather
low NaCl concentration would quickly induce the coagulation
of HAs and form large macromolecular structure. With an
increase in pH, the release of protons and dissociation of
functional groups prevent the formation of hydrogen bonds and
could leave the surface molecules more susceptible to
detachment, leading to a relatively lower coagulation rate. At
pH 10.0, an electrostatic repulsion may prevail over the
molecules, as −COOH and phenolic −OH functional groups
become fully negatively charged upon deprotonation and give
rise to a continuous increase in the negative surface charge.
Under such a circumstance, more counterions are needed to
change the electrostatic equilibrium of HA colloids. Tombacz et
al. reported that at a high pH, the functional groups of HAs are
fully ionized and the charges linked by organic structures try to
locate as far as possible from each other.21 This is responsible
for the highest coagulation value in alkaline solution (between
116.0 mM and 127.6 mM). The contribution of hydrogen
bonds may account for the significant pH-dependent variance
observed in the final maximum aggregate <Rh> in Table 2.
Morphology of HA. DLS is a powerful technique for
determining the size and size distribution of nanoparticles at
microscale. By using DLS, the detailed coagulation information
of HAs in solutions can be obtained. The DLS results may also
be related with the TEM observations and give more efficient
information on the morphology of HAs.46,56 HA macromolecules are predominantly globular aggregates with a ringlike structure of rough periphery at pH 5.26. The rough
morphology and hydrogen forces make HAs more susceptible
to be attached by other aggregates, resulting in higher
coagulation rates. Smooth spherical particles are formed in
alkaline solution due to relatively higher electrostatic repulsion
forces.
Implications of This Work. Since the coagulation
behaviors of HAs strongly influence the pollutant adsorption,
distribution and removal in environmental remediation, this
work is of high significance. Our results show that the HA
coagulation is dependent highly on solution chemistry. The
surrounding pH, protonation/deprotonation states of functional groups as well as metal complexation/bridging effects
could influence the coagulation behaviors of HAs. The
evolutions of HA colloids are attributed mainly to the
physicochemical changes of the molecules. Nucleophilic
reactive groups, for example, −COOH, phenolic-, and aliphatic
−OH, in HAs and fulvic acids are reported to adsorb and
produce chemical changes to different contaminants, for
example, metals, pesticides, and nanoparticles.1,2,4 For example,
at a lower pH, more atrazine (a common pesticide) was found
to bind with HAs and the rapid formation of HA aggregates
could help temporarily trap more atrazine, thus reducing its
toxic properties.57 An analysis on the HA coagulation processes
in electrolyte solutions may also provide insights into HAsinduced membrane fouling in seawater desalination and in the
processes associated with filtration of natural water under
seasonal eutrophication.24−26 Therefore, the results of this work
might facilitate a better understanding of the coagulation
coagulation kinetics at pH 7.1 was observed at higher NaCl
concentrations (94.4 to 380.5 mM) (Figure 1 and Table 1),
which is a typical feature for the DLCA regime. However, the
coagulation profiles in the presence of 84.4 mM NaCl could
not be well fitted by neither DLCA model nor RLCA model.
The total interaction potential between soft clusters (e.g., HA
and microgel particles) is different from that for rigid
nanoparticles, where interpenetration effect, for example,
osmotic and elastic potentials, should be taken into account
and the binding forces within the clusters might be
weaker.49−51 Thus, when there is a finite interparticle attraction
energy, for example, at a lower electrolyte concentration,
unbinding and breaking of clusters would occur, resulting in
reversible aggregation, that is, aggregates may dissociate
spontaneously.49−52 Figure 1 shows that in the presence of
84.4 mM NaCl, <Rh> gradually increased in the early
coagulation process, while remained almost unchanged after
2000 s. This could be explained by that at later coagulation
stage, the formed clusters started to disaggregate and finally the
aggregation and disaggregation rates reached a dynamic
equilibrium. As the NaCl concentration was increased from
94.4 to 380.5 mM, the coagulation could be fitted by typical
power-law kinetics well. In comparison, the modeled df values
(Table 1) were larger than those for typical DLCA (df = 1.85 ±
0.1)35−37 and other reported mass fractal dimensions of HS,38
implying their relatively more compact structure. The possible
explanation for the discrepancy in df might be the soft
characters and lower rigidity of biological molecules compared
to engineered colloids, which results in weaker clusters and
restructuring of the colloids.50,51
Effect of Mg2+ on HA Coagulation. HA colloids exhibit
different coagulation behaviors induced by typical divalent
electrolyte MgCl2.32,33 The main difference between the
coagulation behaviors of HAs and that of other nanoparticles
(e.g., Ag nanoparticles and carbon nanotubes) is the
disappearance of gradual increase in <Rh> at the early stage
of agglomeration at pH 7.1 (Figure 4), implying that a rapid
coagulation occurs instantly after the dose of Mg2+. For
engineered nanoparticles with rigid structures, the effect of
dosing divalent cation Mg 2+ is predominantly charge
neutralization,33 which is considerably different for HAs. The
interactions between Mg2+ and HAs include (1) electrostatic
interactions between Mg2+ and the negatively charged functional groups; and (2) complexation/bridging effect of carboxyl,
phenolic groups with Mg2+.1,5 Compared to monovalent
cations, divalent cations can screen charges and reduce
repulsion forces more effectively, which has been confirmed
by the electrophoretic mobility measurements. Complexation
of Mg2+ and HAs promotes the formation of micellar structure
with intramolecular rearrangement, leading to an increased
aggregate size, as evidenced in Figure 4 and Table 2. Bound
divalent cations could form intra and/or intermolecular bridges
between adjacent HA colloids, and as a result increase the
attractive intermolecular forces. Thus, divalent Mg2+ is
considered to be rapidly adsorbed onto the HA molecules,
and the combined effects of charge screening, complexation as
well as bridging facilitate coagulation of HAs in the presence of
Mg2+ at a lower electrolyte concentration.
Effect of pH on HA Coagulation. The coagulation
kinetics of HAs is also found to be pH dependent. HA colloids
are stabilized by some weak forces such as dispersive
hydrophobic interactions (i.e., van der Waals, π−π, and CH-π
bondings) and hydrogen bonds.18,19,53 The latter is pro5047
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■
ASSOCIATED CONTENT
S Supporting Information
*
X-ray photoelectron spectra of HAs; high resolution 1 s XPS
spectra of C, O, and N in HAs; binding energies (eV) and
assignment/quantization of XPS spectral bands; FTIR spectra
of HAs at pH 1.7−10.04; infrared absorption bands of HA;
titration results for HAs calculated with PROTOFIT; negative
charge of HAs as a function of pH; parameters for proton
binding in the NICA-Donnan model; HA coagulation
observations. This information is available free of charge via
the Internet at http://pubs.acs.org/.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:xdye@ustc.edu.cn (X.-D. Y.); hqyu@ustc.edu.cn (H.Q. Y.).
Author Contributions
Long-Fei Wang and Ling-Ling Wang contributed equally to this
work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank Dr. Ming-Quan Yan from Department of Environmental Engineering, College of Environmental Sciences and
Engineering, Peking University for his valuable review comments. We also wish to thank the Natural Science Foundation
of China (51129803 and 21274140) and the Program for
Changjiang Scholars and Innovative Research Team in
University, China for the partial support of this work.
■
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